Opaque liquid detergent compositions



United States Patent 3,2033% OPAQUE LIQUID DETERGENT CGIVIPOSITEONS Frank E. Carroll, Glen Rock, NHL and Ralph E. Sepul- Veda, Bronx, N.Y., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Filed Aug. 18, 1961, Ser. No. 132,289 2 Claims. (Cl. 252-110) The present invention relates to liquid detergent compositions and more particularly to opaque liquid detergent compositions especially adapted for the cleansing of hard surfaces.

While translucent or transparent liquid synthetic detergent compositions are known, the provision of opaque liquid detergent compositions is desirable in that such compositions present a more attractive and more viscous appearance which the consumer associates with greater cleansing power. The formulation of opaque liquid detergent compositions, however, is not a simple matter. Thus if one attempts to prepare opaque liquid detergent compositions by adding opacifying agents to clear hard surface liquid cleansers, the resulting products are unsatisfactory due to their instability. This is brought on by the coagulation and separation of the opacifying agents from the liquid.

It is, therefore, an object of the present invention to provide opaque liquid detergent compositions especially adapted for the cleansing of hard surfaces. Another object is to prepare opaque liquid detergent compositions which are free of coagulation and phase separation and hence are stable. These and other objects of the present invention will be apparent as the description proceeds.

It has now been found that stable, opaque liquid detergent compositions are formed when certain soaps, a nonionic detergent and a complex phosphate are combined in critical proportions in an aqueous medium. The explanation for this phenomenon is not clearly known, but it is believed that a physical complex resulting in an opaque liquid occurs when these ingredients are combined. The foregoing ingredients supply the cleaning, wetting, and foaming properties of the liquid. In addition, other ingredients, such as anionic detergents, sequestering agents, dyes and perfume, may be added, if desired.

Suitable soaps are the salts of fatty acids having from 16 to 18 carbon atoms, for example, the sodium, potassium and ammonium salts of tallow fatty acids (40 iodine value), palmitic acid, oleic acid and stearic acid.

The nonionic detergent may include the monoand di-lower alkylolamides of fatty acids having from 12 to 18 carbons, the condensation product of lauryl alcohol with about 5 moles of ethylene oxide, and nonylphenol condensed with from 1 to 5 moles of ethylene oxide. Examples of suitable alkylolamides include lauric diethanolamide (LDA), lauric isopropanolamide (LIPA), oleic diethanolamide (ODA), myristic diethanolamide (MDA), tallow diethanolamide (TDA) and lauric monoethanolamide (LMEA).

The complex phosphate component may be tetrapotassium pyrophosphate or pentapotassium tripolyphosphate.

The amounts of the components present in the compositions will vary with the specific phosphate, the nonionic detergent, the type of soap and its cation, and the 3,2033% Patented Aug. 31, 1965 lCe total concentration of soap and nonionic detergent. No general relationship can be established for combining soap, complex phosphate and nonionic detergent to give an opaque liquid.

The degree of opacity also varies with the type of soap, the type of nonionic detergent and the concentration of phosphate, the liquids formed ranging from transparent cloudy liquids to transparent opaque liquids to very opaque liquids. A liquid is described as a transparent cloudy liquid if the outline of an object held behind a 4 ounce sample bottle of the liquid can be seen on looking through the liquid even after the liquid has been gently agitated. If an object held behind a 4 ounce sample bottle of the liquid can be seen on looking through the liquid which has stood overnight but it cannot be seen after gentle agitation of the liquid, due to its increase in opacity, the liquid is characterized as a transparent opaque liquid. If an object held behind a 4 ounce sample bottle of the liquid cannot be seen on looking through the liquid after allowing the liquid to stand overnight, the liquid is described as an opaque liquid.

Taking the above variables into consideration, the compositions of the present invention comprise a total of from about 3.5% to about 14% by weight of soap plus nonionic detergent, and from about 5% to about 20% TABLE I.LIQUID COMPOSITIONS CONSISTING OF LDA, TALLOW SOAP, TKPP AND WATER Percent by weight Ingredients. D 4 H a LDA- 4 4 4 Na tallowate Na laurate- TKPP Water Viscosity (cps) Description of composition:

1 Transparent. slightly turbid liquid. 2 Solid paste. 3 Clear homogeneous liquid. 4 Clear homogeneous liquid. 5 LDA separates as solids at top of liquid. 6 Slightly cloudy transparent gell. 7 Clear homogeneous liquid. 8 Opaque liquid.

The data in the foregoing table show that an opaque liquid is formed when lauric diethanolamide, sodium tallow soap and tetrapotassium phosphate are combined in an aqueous medium. The behavior of the individual components in water (Examples A, B, and C) or of combinations of two of the ingredients (Examples D, E, and F) would not indicate that an opaque liquid could be formed by combining the three components. Examples G establishes that even when the three components are present, the particular soap employed is critical to the formation of an opaque liquid. Example H is an opaque liquid detergent composition according to the present invention.

The following table lists compositions based on lauric isopropanolamide (LIPA), sodium tallow soap, tetrapotassium pyrophosphate (TKPP) and water.

TABLE II.LIQUID COMPOSITIONS CONSISTING OF LIPA, TALLOW SOAP, TKPP AND WATER Percent by weight Ingredients K 3 M Viscosity (cps) Description of composition:

1 LIPA separates from liquid. 2 Transparent gell. 3 LIPA separates from liquid. 4 Separates into two nearly equal layers. 5 Opaque liquid.

The data in this table are similar to that of Table I in that the behavior of the individual components in water or combination of two of them would not indicate that an opaque liquid could be formed by combining the three components. Example M of the invention compared with Example L demonstrates that the soap, nonionic detergent and complex phosphate must be selected in accordance with the present invention in order to form an opaque liquid.

The liquid compositions described herein were made by dissolving the soap in water or by neutralizing the fatty acid with an alkali metal or ammonium hydroxide to form soap. The nonionic detergent was then added to the soap solution followed by the complex phosphate which had been predissolved in water. The liquid compositions can also be made by adding the complex phosphate, predissolved in water, to the soap solution followed by the nonionic detergent. Heat was used when necessary todissolve the soap, to melt the nonionic detergent and to facilitate the mixing of the ingredients.

An example of a formulation containing an anionic detergent, sequestering agent and perfume is as follows:

Example N Ingredients: percent by weight Sodium dodecylbenzene sulfonate 1.25 Ammonium tallow soap (40 IV) 2.95 Lauric diethanolamide 2.85 Lauric isopropanolamide 1.00 Tetrapotassium pyrophosphate 10.00 Versene (ethylene diamine tetraacetic acidsequestering agent) 0.10 Perfume 0.15 Miscellaneous 0.40

Water pI-I (as is)10.6 Viscosity (c.p.s.)120.0 Specific gravity1.090

The dodecylbenzene sulfonic acids and tallow fatty acids used in this example were neutralized with 0.63 of ammonium hydroxide, assaying 28% NH:.;, and 1.13% of 50% sodium hydroxide solution. The ammonium and sodium cations are believed to be combined as shown in the above formulation. In addition, the ammonia gives the product an ammoniacal odor.

The following example illustrates the use of pentapotassium tripolyphosphate.

4 Example 0 Ingredients: percent by weight Ammonium tallow soap (40 IV) 2.95 Lauric diethanolamide 2.85 Lauric isopropanolamide 1.00

Pentapotassium tripolyphosphate (anhydrous) 10.00 Distilled water, to 100%.

The pH of the foregoing composition was adjusted to 10.5 by addition of ammonium hydroxide.

Small amounts of sodium pyrophosphate or sodium tripolyphosphate may be added to the compositions of the present invention. While it is difiicult, in view of the aforementioned variables to specify an exact limit for these additives, the amount can be at least that which is equivalent in sodium content to the amount of sodium soap in the formula, if the sodium soap is replaced by a potassium soap.

The following examples further illustrates the present invention without, however, limiting the same thereto. In these examples the total concentration of nonionic detergent plus soap is indicated and for various ratios of nonionic detergent to soap within this concentration, the concentrations of complex phosphate which produce opaque liquid detergent compositions are indicated. By plotting the ratio of nonionic detergent to soap against complex phosphate concentration and connecting the points, a polygonal figure is obtained. Any point within the perimeter of the polygonal figure so obtained will produce an opaque liquid detergent and it is the area within such perimeter which is the subject matter of the present invention. In the following examples, the abbreviations used for the alkylolamides are those identified herein above while NPE-l and NPE-S represent nonylphenol condensed with 1 and 5 moles of ethylene oxide, respectively.

Combined Ratio TKPP Example Ingredients concennonionic concentration, detergent: tration, percent soap percent 1 LDA-ammonium 3. 5 90:10 5 tallow soap. :20 5-10 50:50 l2%-17% 40:60 15-20 30:70 20 2 LDA-ammonium 7 :10 5 tallow soap. 80:20 5-10 70:30 (34-12% 60:40 7 /-15 50:50 8%-17% 40:60 10-20 30:70 12%-17 /j 20:80 3 LDA-ammonium 15 90:10 5 tallow soap. 80:20 5-10 70:30 (SM-12% 60:40 7 /r-15 50:50 8%16% 40:60 10-17% 30:70 10-17 20=s0 1017%, 4 LDA-ammonium 3. 5 80:20 10 oleate soap. 20:80 15 5 LDA-ammonium 14 80:20 5-10 oleate soap. 20:80 5-10 LDA-ammonium 3. 5 80:20 5-10 palmitate soap. 70:30 7 A-15 60:40 10-20 20:80 20 7 LDA-a nmonium 14 80:20 5-10 palnntate soap. 60:40 8%15 20:80 15-20 8 LDA-ammonium 3. 5 80:20 5-10 stearate soap. 60:40 10-15 20:80 20 9 LDA-ammonium 14 80:20 5-10 stearate soap. 60:40 10-15 10 LDA sodium tallow 3. 5 80:20 10 soap. 70:30 10-15 40:60 13%20 30:70 15-20 11 LDA-sodium tallow 14 80:20 10 soap. 70:30 10-15 30:70 15 12 LDA-sodium oleate 3. 5 80:20 5-10 soap. 30:70 15 13 LDA-sodium oleatc 14 80:20 5-10 soap. 30:70 15 Combined Ratio TKPP Combined Ratio TKPP Example Ingredients coneennom'onic concen- Example Ingredients eonoennonioru'e concentratlon, detergent: tration, tration, detergent: tration, percent soap percent percent soap percent 5 14 LDA-sodiumpalmi- 3.5 80:20 10 47 ODA-ammonium 14 80:20 10 tote soap. 70:30 10-15 tallow soap. 60:40 5-10 30:70 18-20 40:60 5-10 20:80 20 20:80 10 15 LDA-sodiumpahni- 14 30:20 10 tate soap. 10:30 7-12 48 ODA-sodmm 3.5 70:30 5-10 30:70 13-18 10 tailow soap. 30:70 13-15 16 LDA-potassiumtal- 3.5 8230 10-15 20:80 15 low soap. 15-20 17 LDA-potassiumtal- 14 70:30 712% 49 ODA-sodium 14 80:20 10 low soap. 30:70 12% tallow soap. 70:30 -11 18 LD1A-%)otassium 3.5 38:20 5-10 30:70 12%l5 0 ea e soap. 0 15 19 LDA-potassium 14 80:20 5-10 0 ODA-p assium 3.5 70:30 5-10 oleate soap. 30:70 tallow soap. 30:70 10-15 20 LDA-potassium 3.5 70:30 7%-15 palmltate soap. 30:40 20 51 ODA-potasslum 14 70:30 5-10 21.. LDi-potassium 14 58:30 7-12% tallow soap. 30:70 10-12% a mi a e soap. 0 -18 22 LFPA-ammonium 3.5 60:40 5-10 52 BrijBO-ammonium 3.5 80:20 5

tallow soap. 40:60 5-15 ow soap. 0 IPA 14 38 28 2'20 20 20:80 H5 23 L -ammon1llm 5 tallow soap. 60:40 5-10 53 BrijBO-ammonium 14 70:30 5 ggo 5-15 tallow soap. 20:80 5-10 0 5-17 24 LIPAammonium 3.5 80:20 54 NPE-Lammonium 3.5 30:70 5

palmitate soap. 28:50 5-10 tallow ap- 2 0 5 2s LIPA-ammonium 14 00:40 5-10 25 55 NPE-l-ammonium 14 :70 5-10 palmitate soap. go 545 tallow soap.

: 0 5 26 LIPA-ammom'um 3.5 60:40 5-10 56 NPE 5-ammonium 3.5 50:50 5-10 stearate soap. 30:70 10 tanow SOEP- 30270 27 iiigigga gi 14 512 57 NPE-5-ammoniun1 14: 50:50 5-10 28 LIPA-sodium 3.5 50:50 5-10 30 tallow soap. 30:70 5-10 tallow soap. 30:70 10-17% 29 LIPAsodium 14 00:40 10 tallow soap. 50:50 5-12 We clalmz 30 LIPA p0tasSium 5 ig 1. A stable opaque liquid detergent composition in the tallow stoap 14 28:70 104715 form of an aqueous solution consisting essentially of: 31 t iiwssiif 3 3; (a) a Water-soluble soap selected from the group consist- 32 LltflfiA-ammonium 3.5 38 5 ing of sodium, potassium and ammonium salts of fatty a W soap M8 5 3 acids having from 16 to 18 carbon atoms, (b) from about 33 LMEA Onmm 14 28328 15 5% to about 20% by weight of a complex inorganic n 111105 313,. 50250 3 polyphosphate selected from the group consisting of tetragfgg potassium pyrophosphate and pentapotassium tripolyphos- 34 MBA-ammonium 3 g Q 5 phate, and (c) a synthetic nonionic detergent selected 110W $8358 12 from the group consisting of lauric diethanolamide, lauric 35 MBA-ammonium 14 {mm i isopropanolamide, oleic diethanolamide, myristic dietha- Soapggfgg 83g nolamide, tallow diethanolamide and lauric monoetha- 36 MBA-sodium 3.5 M noiamide, the amount of soap and nonionic detergent 37 gggfggggg- 14 ggfzg 13 taken together being from about 3.5% to about 14% tallow soap. 70 H5 weight of the total composition and the weight ratio of 30:70 15 38 M?fi potassium 3.5 gg g 13 28213115) ggtergent to soap being from about 90.10 to a ow soap. 0 -15 I 39 MDAmotasgium 14 W30 H0 2. An opaque liquid detergent composition consisting tallow soap. 30:70 10-15 essentially of an aqueous solution of about 1.25% by TDA ammonium 3 5 80:20 540 Weight of sodium dodecylbenzene sulfonate, about tallow soap. 00:40 5-15 2.95% by weight of ammonium tallow soap, about 40:60 1548 r 2.85% by weight of lauric diethanolamide, about 1% 41 TDA-ammonium 14 80:20 5-10 lauric isopropanolamide, about 10% by Weight of tetra- 1 5. otassium r0 hos hate, and about 0.10% b wei ht 40.00 104% P Py P P Y g 42 TBA 5mm 3 5 70 3O HZI/ of the tetrasodium salt of ethylene diamine tetracetic acld.

40160 18 References Cited by the Examiner 3 33311 14 583;? 5g UNITED STATES PATENTS 40160 17% 2,560,839 7/51 Ayo et a1. 252-110 44 TBA-potassium 3.5 :30 5-15 2,674,580 4/54 Henkin.

. l" tallwswp- 40-60 1018 2,920,045 1/60 Hearn et a1. 45 TBA-potassium 14 70:30 5-15 3,021,284 2/62 Doan 252- tallow soap. 30:70 17% 60 4s ODA-ammonium 3.5 egv g 540V JULIUS GREEN WALD, Primary Examiner.

tallow soap. 4 5-12 2 20180 15 ALBERT T. MEYERS, Exammer. 

1. A STABLE OPAQUE LIQUID DETERGENT COMPOSITION IN THE FORM OF AN AQUEOUS SOLUTION CONSISTING ESSENTIALLY OF: (A) A WATER-SOLUBLE SOAP SELECTED FROM THE GROUP CONSISTING OF SODIUM, POTASSIUM AND AMMONIUM SALTS OF FATTY ACIDS HAVING FROM 16 TO 18 CARBON ATOMS, (B) FROM ABOUT 5% TO ABOUT 20% BY WEIGHT OF A COMPLEX INORGANIC POLYPHOSPHATE SELECTED FROM THE GROUP CONSISTING OF TETRAPOTASSIUM PYROPHOSPHATE AND PENTAPOTASSIUM TRIPOLYPHOSPHATE, AND (C) SYNTHETIC NONIONIC DETERGENT SELECT FROM THE GROUP CONSISTING OF LAURIC DIETHANOLAMIDE, LAURIC ISOPROPANOLAMIDE, OLEIC DIETHANOLAMIDE, MYRISTIC DIETHANOLAMIDE, TALLOW DIETHANOLAMIDE AND LAURIC MONOETHANOLAMIDE, THE AMOUNT OF SOAP AND NONIONIC DETERGENT TAKEN TOGETHER BEING FROM ABOUT 3.5% TO ABOUT 14% WEIGHT OF THE TOTAL COMPOSITION AND THE WEIGHT RATIO OF NONIONIC DETERGENT TO SOAP BEING FROM 90:10 TO ABOUT 20:80. 